The impact of sequestration on the bioaccessibility of arsenic in long-term contaminated soils

Arsenic (As) contamination of soil poses a potential threat to human health, particularly for small children, through the incidental ingestion of soil from hand-to-mouth activity. In this study, we examined the relationship between As bioaccessibility using the simplified bioaccessibility extraction test (SBET) and the soil fractions that contribute to bioaccessible As in 12 long-term contaminated soils. Sequential fractionation of soils prior to As bioaccessibility assessment found that As was primarily associated with the specifically sorbed (3-26%), amorphous and poorly crystalline (12-82%), and the well crystalline (3-25%) oxyhydroxide Fe/Al phases with proportions varying depending on the mode of As input. Arsenic bioaccessibility in these soils ranged from less than 1% in the gossan soil to 48% in railway corridor soils. Soil fractions contributing to As bioaccessibility were found to be from the non-specifically (<1-11%), the specifically (<1-29%) sorbed and the amorphous and poorly-crystalline (30-93%) oxyhydroxide Fe/Al fractions. Significant correlations (p<0.05) were found between the As bioaccessible fraction and the amorphous and poorly-crystalline oxyhydroxide Fe/Al fractions indicating that this fraction is a key factor influencing As bioaccessibility in many anthropogenically contaminated soils.     

Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis

Pine wood, pine bark, oak wood and oak bark were pyrolyzed in an auger reactor. A total of 16 bio-oils or pyrolytic oils were generated at different temperatures and residence times. Two additional pine bio-oils were produced at the National Renewable Energy Laboratory in a fluidized-bed reactor at different temperatures. All these bio-oils were fractionated to obtain lignin-rich fractions which consist mainly of phenols and neutrals. The pyrolytic lignin-rich fractions were obtained by liquid-liquid extraction. Whole bio-oils and their lignin-rich fractions were studied as potential environmentally benign wood preservatives to replace metal-based CCA and copper systems that have raised environmental concerns. Each bio-oil and several lignin-rich fractions were tested for antifungal properties. Soil block tests were conducted using one brown-rot fungus (Gloeophyllum trabeum) and one white-rot fungus (Trametes versicolor). The lignin-rich fractions showed greater fungal inhibition than whole bio-oils for a impregnation solution 10% concentration level. Water repellence tests were also performed to study wood wafer swelling behavior before and after bio-oil and lignin-rich fraction treatments. In this case, bio-oil fractions did not exhibit higher water repellency than whole bio-oils. Comparison of raw bio-oils in soil block tests, with unleached wafers, at 10% and 25% bio-oil impregnation solution concentration levels showed excellent wood preservation properties at the 25% level. The good performance of raw bio-oils at higher loading levels suggests that fractionation to generate lignin-rich fractions is unnecessary. At this more effective 25% loading level in general, the raw bio-oils performed similarly. Prevention of leaching is critically important for both raw bio-oils and their fractions to provide decay resistance. Initial tests of a polymerization chemical to prevent leaching showed some success.     

Polybrominated diphenyl ethers and HBCD in bird eggs of South Africa

In this paper, the first data on brominated flame retardants (BFRs), in particular polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in eggs of bird species from South Africa are described (N=43). Concentrations of PBDEs were detected in all the studied species and in all the geographic areas. Highest concentrations of PBDEs were measured in bird eggs from the Vaal River, which is situated downstream of the most industrialized area in South Africa. Sum-PBDE concentrations were highest in eggs of one African sacred ibis (396 ng g(-1) lipid weight (lw)), possibly due to foraging on dumping sites. Lowest mean level of sum-PBDEs (2.3 ng g(-1) lw) was measured in cattle egrets (N=11) from Barberspan Sanctuary, a Ramsar site. The PBDE congener pattern showed large differences, reflecting different trophic levels, migratory behavior, distance to the source, and, exposure to different PBDE mixtures, among others. HBCD was detected only in four species, and highest levels were measured in one egg of African sacred ibis (71 ng g(-1) lw). In most species, levels of PBDEs were one to several orders of magnitude lower than levels of DDTs and PCBs. PBDEs correlated strongly with DDTs, PCBs and some other organochlorines (OCs), indicating the same source. The widespread occurrence of PBDEs in the South African avian species showed a strong need for further investigations of PBDEs in the Southern African environment.     

Identification of key parameters controlling dissolved oxygen migration and attenuation in fractured crystalline rocks

In the crystalline rocks of the Canadian Shield, geochemical conditions are currently reducing at depths of 500-1000 m. However, during future glacial periods, altered hydrologic conditions could potentially result in enhanced recharge of glacial melt water containing a relatively high concentration of dissolved oxygen (O2). It is therefore of interest to investigate the physical and geochemical processes, including naturally-occurring redox reactions, that may control O2 ingress. In this study, the reactive transport code MIN3P is used in combination with 2k factorial analyses to identify the most important parameters controlling oxygen migration and attenuation in fractured crystalline rocks. Scenarios considered are based on simplified conceptual models that include a single vertical fracture, or a fracture zone, contained within a rock matrix that extends from the ground surface to a depth of 500 m. Consistent with field observations, Fe(II)-bearing minerals are present in the fractures (i.e. chlorite) and the rock matrix (biotite and small quantities of pyrite). For the parameter ranges investigated, results indicate that for the single fracture case, the most influential factors controlling dissolved O2 ingress are flow velocity in the fracture, fracture aperture, and the biotite reaction rate in the rock matrix. The most important parameters for the fracture zone simulations are flow velocity in the individual fractures, pO2 in the recharge water, biotite reaction rate, and to a lesser degree the abundance and reactivity of chlorite in the fracture zone, and the fracture zone width. These parameters should therefore receive increased consideration during site characterization, and in the formulation of site-specific models intended to predict O2 behavior in crystalline rocks.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Substance Flow Analyses of Organic Pollutants in Stockholm

This paper summarizes substance flow analyses for four organic substances in the City of Stockholm, Sweden: diethylhexyl phthalate (DEHP), alkylphenolethoxylates (APEO), polybrominated diphenylethers (PBDE) and chlorinated paraffins (CP). The results indicate that the stocks of APEO, PBDE and CP all are approximately 200–250 tonnes, whereas the DEHP stock is two orders of magnitude larger. Emissions can be linked to imported consumer goods such as electronics (PBDE) and textiles (APEO), and to construction materials (DEHP, CP). For several of the substances considerable amounts remain in the technosphere for a long time, even after use of the substance in new products has been eliminated. For example, the use of DEHP as plasticizer for PVC plastics in cables and floorings has more or less been phased-out, but still these applications make up a stock of some 20,000 tonnes (85% of the total DEHP stock in Stockholm) and emit 28 tonnes of DEHP annually (93% of overall emissions). Likewise, the use of chlorinated paraffins in sealants has been radically reduced, but there are 170 tonnes of CP in sealants in Stockholm making up 75% of the stock, and causing half of the emissions to water and air. These emissions are likely to continue for decades, and the stocks therefore have to be considered when analysing and managing the impact of urban substance flows on the environment.     

Monopolization in a resource queue: water striders competing for food and mates

The monopolization of resources plays an important theoretical role in the literature on competition for food and mates. We used 12 groups of male water striders (Aquariusremigis) to: (1) test the general prediction that monopolization of both food and mates decreases as the temporal clumping of resources increases, (2) compare the efficiency of two indices of resource monopolization, coefficient of variation and Q (Ruzzante et al. 1996), and (3) quantitatively assess the resource queue model of Blanckenhorn and Caraco (1992). Each group of six males competed for both food items and mates released from the upstream end of a laboratory stream. The mean inter-arrival time for resource units (food or females) was 10 min, with four levels of temporal clumping (variance in inter-arrival time: 0, 25, 50 or 320 min²). As predicted, the monopolization of both food and mates decreased as the temporal clumping of resource arrival increased, although monopolization was greater for food than for mates. Q detected the difference in monopolization of food and mates, whereas the coefficient of variation did not, because Q is independent of mean resource abundance. The resource queue model successfully predicted monopolization of both resource types, explaining 89% and 76% of variation in the proportion of food and mates acquired by the six males. The success of the model suggests that the scaling of handling time to the variance in resource inter-arrival time should play an important role in any general theory of resource monopolization. Received: 28 February 1997 / Accepted after revision: 26 September 1997     

Bushcricket song structure and predation by the acoustically orienting parasitoid fly Therobia leonidei (Diptera: Tachinidae: Ormiini)

Males of most bushcricket species produce acoustic advertisement signals to attract females for mating. These signals can also increase conspicuousness to predators. In the genus Poecilimon (Orthoptera: Phaneropterinae) males are attacked by the parasitoid fly Therobia leonidei (Diptera: Tachinidae: Ormiini) which locates males by their calls. In Greece T.leonidei parasitizes several Poecilimon species with different song structures: we examined whether host choice is related to song structure by comparing parasitism rates in two closely related Poecilimon species. One of these species produces monosyllabic songs, the songs of the other species being polysyllabic. The tachinid fly parasitized the polysyllabic species to a greater extent. We demonstrate in a field-experiment that this preference for the polysyllabic species does not depend on local adaptations of the fly. The most probable explanation for the preference of the fly for the polysyllabic singing species seems to be better detection of longer songs. This result is discussed in the context of male song evolution. Received: 4 November 1997 / Accepted after revision: 22 March 1998     

Molecular response of the sponge Suberites domuncula to bacterial infection

The aim of this study was the documentation of the molecular immune response of Suberites domuncula upon bacterial infection. Additionally, the bacteria that are naturally present in the sponge after prolonged aquarium maintenance were characterized. After 6 months of maintenance of S. domuncula in seawater aquaria, only one bacterial 16S rDNA sequence could be recovered, which belongs to the genus Pseudomonas. Concomitantly, morphologically uniform bacteria were found encapsulated in bacteriocytes. These findings indicate that certain bacteria, possibly of the genus Pseudomonas, are able to persist for long periods in host bacteriocytes. Subsequent to performing a previously established infection assay with S. domuncula, a potentially pathogenic Vibrio sp. was isolated from the tissues. Furthermore, the host tissue disintegrated and asexual propagation bodies (gemmules) were formed. In order to gain insights into the molecular events occurring after bacterial infection, the stress-response kinases, p38 protein kinase and JNK protein kinase, were analyzed. It is demonstrated that these two kinases are activated (phosphorylated) upon incubation of the tissue with the bacterial endotoxin lipopolysaccharide (LPS). Moreover, LPS strongly inhibits protein synthesis. It is concluded that there are many functionally different interactions between S. domuncula and bacteria and that the animal possesses mechanisms to differentiate between bacteria and to respond accordingly.